If clubs give the go-ahead, top-flight matches could take place on Mondays from February 8, the RFEF said on its website.
"It's clear this move was needed to extend the range of what is offered on television because the Spanish league was at a disadvantage compared to other championships like the (English) Premier League and the (German) Bundesliga," LFP vice president Javier Tebas told As newspaper on Wednesday.
"Many clubs are due to renew their TV contracts in 2011 and this agreement will allow them to be worth much more than they would have done."
The deal between the RFEF and LFP also foresees playing one second-division match on Fridays.
Tebas dismissed the claim that staging matches on Mondays for two seasons in the 1990s had not been a success.
"I am sure Monday is a great day for people to watch football because many are at home and you could say the same about Fridays," he told As.
The LFP has also been mulling the idea of staging weekend La Liga matches earlier so that Asian viewers can see them more conveniently, a move supported by clubs like Real Madrid who want to raise their profile there.
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